Reaction products of dienes and process of producing same



Patented Aug. 14, 1945 UNITED STATES ass'aaos REACTION PRODUCTS OFDIENES AND PROCESS OF PRODUCING SALIE Alexander A. Miller,

Stamford, Conn,

and

Theodore F. Bradley, Edgewood, Md., assi nors to American CyanamidCompany, New York, N. Y., a corporation of Maine No Drawing. Originalapplication March 24, 1943, Serial No. 480,332. Divided and thisapplication July '29, 1944, Serial No. 547,292

2 Claims.

This invention relates to a new series of synthetically preparedmonomeric compounds, especially those obtained by reacting a compoundcontaining one or more conjugated double bonds with an acrylic compound.More particularly, it embraces such compounds asalloocimene-acrylonitrile addition products, myrcene-acrylonitrileaddition products and similar adducts of dieneacrylic compounds and theprocesses for preparin; such compounds.

It is an object of this invention to prepare these diene reactionproducts from relatively inexpensive and readily available rawmaterials.

It is a further object to prepare such products to serve as valuableintermediates suitable for use in the preparation of coatingcompositions, metallic driers, plasticizers, and the like.

Still another object is to provide a process for the reaction of trienessuch as alloocimene, myrcene and the like with vinyl compounds such asacrylonitrile.

These and other objects are attained by reacting the particular dienecompounds with acrylonitrile by heating equimolecular mixtures thereofunder such conditions as those described in the accompanying examplesforming a part of this invention.

The resultant compounds prepared as described below serve asintermediates for the production of a numberv of useful industrialcompounds. The monomeric products of this invention as well as some ofthe polymeric compounds obtained therefrom havea wide field ofapplication such, for example, as modifiers for plastics, plasticizersfor natural and synthetic rubber, adhesivesand the like. Whenincorporated in such solvents as, for example, xylene, toluene, ketones,ethyl dichloride and the like, useful and valuable coating compositionsare obtained.

The nitriles, amines alcohols, acids and esters of the abovediene-acrylonitrile adducts also have a wide variety of commercialapplications. For example, the nitriles and amines are usefulinsecticides and insect repellents. In particular, such derivatives as5,5-dimethyl-2- (ix-methyl propenyl) =3-cyclohexene 1 carbonitrile hasbeen found to be an especially efiective mosquito repellent. The aminesalso find use as surface active agents. The metallic salts of the acidsare useful driers for coating compositions. The esters are valuableplasticizers for gums, resins, natural and synthetic rubber and thelike.

Thus it may be seen that these diene adducts serve as very usefulchemical intermediates and find application for various and sundryindustrial purposes, particularly when prepared in accordance with thefollowing detailed descriptive exbeing illustrative and not limitativeof the invention.

EXAMPLE 1 .Rmc'rron Motions or Annoocnmns AND I Acsvrommr:

Alloocimene 1105 2. (ca. 8 mols) Acrylonitrile 424 g. (ca. 8 mols)Hydroquinone 1.5 g. (ca. .1%)

The reaction is probably indicated as follows:

on cm 0 o c an on on,

n CHs=CH-CN n n-cN Acrylonitrile n c JF-CH: -CH:

H E (SE: HI

Alloocimene Adduct amples which illustrate specific embodiments of theinvention.

given in parts by weight, the examples themselves This mixture in theform or a solution is heated on an oil bath to C. at which temperatureit refluxes. After refluxing for 60 hours, the temperature will be foundto have risen to 135 0. This indicates that most of the low boilingcomponent, acrylonitrile, has been removed either by reaction with thealloocimene or else by volatilization from the reaction mixture. Thedecrease mene-acrylonitrile adduct is: a

0 06 CH. Hui H-CN Name: 5,5-dimethyl-2-(-methylpropenyl)-3-cyclohexene-l-carbonitrile Molecular weight= 189 Boiling range=-120C./l mm. n =1.'4948 das =0.9107

EXAM-$52105 llonomrc Rxacrrox Plonoc'r or Asnoocnlxils m Acanonrruu UnaSum-Ammo Pussuasconmons In order to decrease the time of reaction be Itween ailoocimene and acrylonitrile, the reaction is preferably carriedout in an autoclave at higher temperatures than those given in Example 1and at super-atmospheric pressure. In order to minimize oxidation andpolymerization, 0.1% hydroquinone is added. The following table gives aseries of ms made at different temperatures and extending over diflerenttime intervals in order to obtain optimum conditions for a maximum yieldof product with a minimum of polymer formation. In each of the examplesgiven below,.

equimolar reacting portions of alloocimene and acrylonitrile are heatedwith .1 to 1% of hydro-- quinone in an autoclave. Fractionation of theresultant product at 1 mm. mercury pressure, eliminating the firstfraction boiling below 100 C. as consisting principally of unreactedmaterial, gives the following results in each example:

Table Autoclave reaction of alloocimene with acrylonitrile product Terip.

. Per.

cent unreacted P81- cent p y B.P.at

Time,

hrs. 1 mm.

is; yield 1 Constant vapor temperature. 1 Product dark yellow in color,indicating temperature of 175 C.

was too high.

Summarizing the results obtained from the table it is seen that heatingthe reactants at 150 C. for 12 hours as in Example 3 results in apreferred yield of the alloocimene-acrylonitrile reaction product.

This mixture is refluxed at first at a temperature of 90 C. Afterrefluxing for a period of four hours it is found that the temperaturerises gradually to 120 0., while the rate of refluxing decreases withthe increasing viscosity of the solution. The resultant product is thenfractionally distilled under a pressure of 1 mm. of mercury, theunreacted myrcene and acrylonltrile beaasasos ing stripped of! at vaportemperatures up to C. The myrcene-acrylonitrile reaction, however, givesmuch higher proportion of undesirable polymer. Thus in the above run 40%of the polymeric and 46% of the monomeric addition prodnot was obtained,while 13% of the myrceneacrylonitrile solution remained unreacted. Thefraction boiling at C. to 123 C./1 mm. pressure yields the desiredproduct. a myrceneacrylonitrile adduct, the major portion of whichdistilis over rapidly at 119-120 C./1 mm. pressure.

is The probable formula of this reaction product CHI-ON Cl CE,

o. cm Name 4-(v-isohexenyl) -3-cyclohexene-1-carhonitrile Molecularweight=189 liioiling range=-120 C./1 mm.

n =1.4895 ds= =os191 EXAMPLE 7 Hxnnoonmnon or Pnonucr or Exams: 1

A sample of the alloocimene-acrylonitrile addition product of Example 1is readily hydrogenated under super-atmospheric pressure with the aid ofRaney nickel as a catalyst. The product possessing a strongly ammoniacalodor is readily separated by filtration from the catalyst to yield acolorless liquid which upon standing exposed to the air becomesreddish-brown in color. The 111- trate is fractionally distilled and theportions boiling at 98 to 100 C./1 mm. pressure comprise 80% of thetotalfiltrate and make up the desired primary amine having the probablestructuralformula:

Cg: /CH! (i'lH: CH: on, cm-cm-Nm H-CH:

Hi. Name: 3,3-dimethyl-6-(sec. butyl) -1-cyclohexanemethylamineMolecular weight =19! Boiling range=98---100v C./1 mm. n ==1.4897dzs=0.8848

The undesired non-volatile residue comprising the remaining 20% is asecondary amine forming no pant of the subject matter of the presentapplication.

EXAMPLE 8 v Hvnaocsm'non or run Pnonucr or Exam 6 1 Themyrcene-acrylonitrile addition product of Example 6 is readilyhydrogenated as above de- 75 scribed in Example 7 and yields a productwhich upon distillation under a pressure of 1 mm. of mercury yields aprimary amine having a boiling point range of 115-120 C./1 mm. pressureat which temperature 84% of .the desired product in the form of aprimary amine distills over. This primary amine has the followingprobable formula:

CH-CHrNHz OH: on:

0m CH3 Name: 4-is0heXyl-1-cyclohexanemethylamine Molecular weight=l97Boiling range=1l5-l20 C./1 mm. n =L4942 d25 =0.894l Neutral equivalent190 (theory 197).

A number of other monomeric materials which may be subsequentlypolymerized, or even used as the monomers, may likewise be obtained byreacting alloocimene, beta-myrcene, etc., with such products asdichloroacrylonitrile, dibromoacrylonitrile, methyl methacrylate, andthe like. Such compounds as the above may be used to form copolymerswith products such as butadiene, isoprene, pentadiene, dimethylbutadiene, chlorobutadienes, and the like. Furthermore, the compounds ofthis invention either in monomeric or in polymeric form may be dissolvedin any one of a number of suitable solvents for use in coatingcompositions, such solvents including toluene, xylene, the ketones,ethyl dichloride, etc. Such coating compositions may have added theretonatural or synthetic drying oils as well as such resinous materials asany one of a number of phenol-formaldehyde condensation resins, moreparticularly such oil-soluble substituted phenol-formaldehydecondensation products as p-tert.-amyl-pheno1 formaldehyde condensates.In addition various other resins such as the aminotriazine-formaldehydecondensation products, polyalcohol-polycarboxylic acid resins eithermodified with a fatty oil acid, ester gum, coumarone-indene resin, or inunmodified form may likewise be used to form coating compositions.

A compatible dye or various pigments may be incorporated in thesecoating compositions, examples being titanium dioxide, zinc oxide, ironoxide, malachite green, toluidine red, ochre, carbon black, etc. Ifdesirable, fillers, extenders and the like may also be included such aswood flour, clay, glass wool, granite dust, sand, etc.

The above examples illustrate clearly that the use of more intensivereaction means such as may be effected with the aid of autoclaves, highpressures, inert gas media, and the like, result in higher yields ofdesired adduct products. Likewise utilizing such intensive reactionsfacilitates the reaction of conjugated fatty acids and their esters aswell as other more readily available dienes with corresponding acryliccompounds.

The resultant monomers are suitable for a wide variety of purposes,particularly in the field of plastics and in the field of coatingcompositions. The products are useful ingredients for paper coating,textile coating or for coating other fibrous materials such as leather,as well as for impregnating and facilitating the penetration of variousresinous materials into and between the fibers of similar fibrousmaterials. The heavy metal salts of acrylic acid-alloocimene additionproducts can be readily prepared by precipitation of such salts from anaqueous solution of a neutral potassium salt of the adduct product bysuch ions as Pb++, Mn++, Co++, Cu++, etc. The lead, man= ganous, andcobalt salts have properties similar to .the corresponding naphthenatesand hence may be incorporated in driers for coating compositions.

The compounds of this invention may be used 7 as plasticizers foradhesives, particularly for such tacky materials as natural andsynthetic rubber in adhesive mixtures.

This application is a division of our application Serial No. 480,332,filed March 24, 1943. Many modifications and variations of the processand compounds described herein above may be made without departing fromthe spirit and scope of the invention as defined in the appended claims.

We claim: 1. A compound having the following probable formula:

cH-cN c on,

being the reaction product of equimolecular proportions of myrcene andacrylonitrile.

2. The process which comprises reacting equimolecular proportions ofmyrcene and a'crylonitrile by heating them together at a temperature ofat least C. v

ALEXANDER A. MIILER. THEODORE I". BRADLEY.

